C6= C3= + C3=

C7= C3= + C4=

C8= C3= + C5= or C4= + C4=
However, various reactions such as bimolecular reaction, isomerization reaction etc occur at the
same time.
Experiments were also conducted on octene isomers in order to confirm the effects of shape
selectivity of ZSM-5. From Figure 3 shows that linear olefins had an even higher conversion than
branched olefins and that the shape selectivity of ZSM-5 has an effect.
In addition, with regards to propylene selectivity, 1-octene and 2-methyl-1-heptene are almost
the same however 2,4,4-trimethyl-1-heptene has a low propylene yield. In this way it can be seen
that as ZSM-5 zeolite shows shape selectivity properties, the products distribution changes
greatly depending on the isomer.
According to Buchanan et al 3), olefins with a relatively low carbon number such as C6 olefin
isomerizes faster than catalytic cracking however the catalytic cracking of C8 olefins is even
faster. Accordingly, it is thought that the difference in isomers will be shown greatly in actual

50

100

40

90

30

80

20

70

10

60

50
2,4,42-methyl1-octene
1-heptene trimethyl1-pentene

Feed

1-hexene 1-heptene
C6=

C7=

Conv. ,wt%

Yields , wt%

FCC reactions with regards to C8 olefin.

T-C2
T-C3
T-C4
T-C5
Conv.
4

C8=

Fig.3 Yields and Conversion for Cracking C6-C8 Olefins

Deactivation (OCTUP-11S) : 750-13hr-100%Steaming
MAT : Rx.Temp.525, C/O 1

5. High activity ZSM-5 additive OCTUP-

5.1 Development concept of OCTUP-
Up until now, JGC C&C has been selling ZSM-5 additive as our OCTUP series. In 2005,
OCTUP-11S with improved pore size distribution and phosphorus modification technology was
developed and commercialized and has a lot of commercial experience in a large number of
refineries in Japan and overseas. We have now newly developed ZSM-5 additive, OCTUP-
with even better performance.
The following four points are considered important points when designing a high activity

ZSM-5 additive: 1) high ZSM-5 zeolite content, 2) ZSM-5 zeolite with high hydrothermal stability,
3) pore size control technology, 4) phosphorous modification technology.

4)

In comparison with

OCTUP-11S, OCTUP- has a higher ZSM-5 zeolite content and by optimizing the pore size
distribution of matrix has been able to surpass those of our existing OCTUP series.
Ordinarily, when the ZSM-5 content increases, the physical properties of the additive (apparent
bulk density, attrition resistance) deteriorate and have a negative effect however JGC C&C has
made it possible to keep these properties by applying their catalyst preparation technology.
With regards to the pore design of ZSM-5 additive, it is important to improve the diffusion of
the reactants (gasoline components) within the pores of ZSM-5 additive. 5) By increasing the pore
volume of OCTUP- the gasoline components become easy to diffuse to the active sites (ZSM-5
zeolite) within the additive pores and is thought to have high performance.
5.2 Solid acid, pore size distribution properties of OCTUP-
The solid acid distribution properties of our conventional OCTUP-11S and our newly developed
OCTUP- are shown in Figure 4.
As OCTUP- has a higher ZSM-5 content than OCTUP-11S, there is more acidity after pseudo
-deactivation. Strong acids and medium acids in particular increased.
Next, the pore size distribution of pseudo-deactivated ZSM-5 additive measured by mercury
porosimetry is shown in Figure 5. Improvement in diffusion of reactants is expected due to
OCTUP- having a larger pore volume in the macropore region of 50nm~200nm than
OCTUP-11S.

0.4
Pore Volume, ml/g

Acidity, mmol/g

0.08
0.06
0.04
0.02
0.00

0.3
0.2
0.1
0

11S

Strong 90kJ/mol
Medium 80-90kJ/mol
Weak 70-80kJ/mol

Fig.4 Solid Acid Distribution of

OCTUP-11S and OCTUP-

11S

Macro Pore 50-200nm

Meso Pore 5.5-50nm

Fig.5 Pore size Distribution of

OCTUP-11S and OCTUP-

measured by Micro Calorymetry of NH3 adsorption measured by mercury prosimetry

deactivated sample : 750-13hr-100% steaming
deactivated sample : 750-13hr-100% steaming

5.3 OCTUP- performance

The results of the pilot tests (Midget) on OCTUP- are shown in Table 1. 6% of